Electrode plate for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery

ABSTRACT

There is disclosed an electrode plate for a nonaqueous electrolyte secondary battery, which comprises a collector and an active material layer provided on at least one side of the collector, in which the active material layer has one or more slits. Such an electrode plate can facilitate infiltration of a liquid electrolyte even when wound at high density and can have high stability of quality. There is also disclosed a nonaqueous electrolyte secondary battery with high capacity and high quality, which is constructed using the above-mentioned electrode plate.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an electrode plate for use innonaqueous electrolyte secondary batteries typically includinglithium-ion secondary batteries and to a nonaqueous electrolytesecondary battery using thereof.

2. Description of the Related Art

Recent years have seen rapid advances in miniaturization and weightreduction of electronic equipment and communication equipment. Thus,there has been a demand for miniaturization and weight reduction ofsecondary batteries for use as a driving power source in such equipment.For this purpose, in place of conventional alkaline storage batteries,there have been proposed nonaqueous electrolyte secondary batteries,typically lithium-ion secondary batteries, which can have a high energydensity and a high voltage.

An electrode plate for use as a positive electrode of the nonaqueouselectrolyte secondary battery (a positive electrode plate) is producedby using a complex oxide such as lithium manganate and lithium cobaltateas a positive active material, dispersing or dissolving the positiveactive material, an electrically-conductive material and a binder in anappropriate wetting agent (solvent) to prepare a slurry-like coatingcomposition, and applying the coating composition onto a collector madeof metal foil so that a positive active material layer is formedthereon.

On the other hand, an electrode plate for use as a negative electrode ofthe nonaqueous electrolyte secondary battery (a negative electrodeplate) is produced by using a carbonaceous material such as carboncapable of occluding cation (such as lithium ion) as a negative activematerial, in which the cation is released from the positive activematerial at the time of charging, dispersing or dissolving the negativeactive material and a binder in an appropriate wetting agent (solvent)to prepare a slurry-like coating composition, and applying the coatingcomposition onto a collector made of metal foil so that a negativeactive material layer is formed thereon.

A terminal for taking out electric current is then attached to each ofthe positive and negative electrode plates, both of which are then woundup with a separator (for preventing short circuit) sandwichedtherebetween and sealed in a container filled with a nonaqueouselectrolyte solution, so that a secondary battery is constructed.

In recent years, there has also been a demand for a nonaqueouselectrolyte secondary battery with higher capacity, and variousimprovements have been made. An example of such improvements is totightly wind the electrode plates for the purpose of increasing theamount of the active material to be stored in the limited volume,namely, a method of increasing the winding density of the electrodeplates. However, an increased winding density can lead to a reduction invoids for infiltration of the liquid electrolyte, so that the liquidelectrolyte can less infiltrate into the active material layer. Suchreduced infiltration of the liquid electrolyte can lead to poor batteryperformance, even if the winding density of the electrode plate isincreased for the purpose of increasing the capacity.

Japanese Patent Application Laid-Open (JP-A) No. 09-129223 discloses amethod of ensuring paths for a liquid electrolyte by embossing theactive material layer. In such a method, however, a load can locally beapplied to projection portions of the embossed material, when theelectrode plates are wound up. Thus, such a method can cause a ruptureof the electrode due to expansion and contraction of the volume duringcharge and discharge cycles and has a problem with stability of quality.

SUMMARY OF THE INVENTION

The present invention has been made in view of the above circumstances.It is therefore a first object of the invention to provide an electrodeplate for nonaqueous electrolyte secondary battery which can facilitateinfiltration of a liquid electrolyte even when wound at high density andcan have high stability of quality.

It is a second object of the invention to provide a nonaqueouselectrolyte secondary battery with high capacity and high qualityconstructed using the above-mentioned electrode plate.

The present invention is directed to an electrode plate for a nonaqueouselectrolyte secondary battery, which comprises a collector and an activematerial layer provided on one side or both sides of the collector, inwhich the active material layer has a slit or slits.

In the electrode plate for a nonaqueous electrolyte secondary battery ofthe present invention, the active material layer has a slit or slits.Such a slit functions as a path for a liquid electrolyte, when theelectrode plates are closely laminated to each other. Such a slit canalso increase the surface area of the active material layer. Even whenelectrode plates wound at a high density are placed in a battery case,the liquid electrolyte can easily infiltrate into the active materiallayer so that charges can rapidly move between the electrodes and that ahigh voltage or a high current can be produced. In addition, the activematerial layer has no projection portion and thus can be free from alocally applied load. Therefore, the electrode can be prevented frombeing ruptured by expansion and contraction of the volume during chargeand discharge cycles and can exhibit high stability of quality.

In another aspect, the invention is directed to a nonaqueous electrolytesecondary battery, comprising the above electrode plate for a nonaqueouselectrolyte secondary battery according to the present invention. Inthis secondary battery, the winding density of the electrode plate canbe increased for the purpose of increasing the capacity, because theelectrode plates packed inside can facilitate infiltration of a liquidelectrolyte even when wound at high density and can have high stabilityof quality. Therefore, in this secondary battery a larger amount of theactive material can be stored in the limited volume, so that the batterycan stably offer high capacity and high quality performance for a longtime.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a diagram schematically showing an example of the slits in theactive material layer according to the present invention;

FIG. 2 is a diagram schematically showing other examples of the slits inthe active material layer according to the present invention;

FIG. 3 is a diagram schematically showing a rotary die unit, which is anexample of the means for forming slits in the active material layeraccording to the present invention.

Additionally, symbols in the figures respectively represent thefollowing meaning: 1 active material layer 2 winding direction ofelectrode plate 3 slit 4 distance between adjacent slits 5 rotary dieunit 6 blade

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The electrode plate for a nonaqueous electrolyte secondary batteryaccording to the present invention comprises a collector and an activematerial layer formed on at least one side of the collector and is suchthat the active material layer has one or more slits.

The electrode plate for a nonaqueous electrolyte secondary batteryaccording to the invention may be any of a positive electrode plate anda negative electrode plate. The positive electrode plate may be producedby applying a positive active material layer coating composition, whichcontains at least a positive active material and a binder, onto one sideor both sides of a corrector, so as to form a positive active materiallayer. The negative electrode plate may be produced by applying anegative active material layer coating composition, which contains atleast a negative active material and a binder, onto one side or bothsides of a corrector, so as to form a negative active material layer.

The positive active material may be any conventional positive activematerial for nonaqueous electrolyte secondary batteries. Examples ofsuch materials include lithium oxides such as LiMn₂O₄ (lithiummanganate), LiCoO₂ (lithium cobaltate) and LiNiO₂ (lithium nickelate);and chalcogen compounds such as TiS₂, MnO₂, MoO₃, and V₂O₅.

The positive active material is preferably in the form of a powderhaving a particle diameter of 1 to 100 μm and an average particlediameter of about 10 μm, in order that it can be uniformly dispersed ina coating layer. One or more of these positive active materials may beused alone or in combination.

The negative active material may be any conventional negative activematerial for nonaqueous electrolyte secondary batteries. Preferredexamples of such materials include carbonaceous materials such asnatural graphite, artificial graphite, amorphous graphite, carbon black,materials wherein a different element is added to any one of thesematerials; and lithium-containing metal materials such as lithium metaland lithium alloys.

The granular shape of the negative electrode-active material is notparticularly limited. Examples thereof include scaly, lump, fibrous, andspherical shapes. The negative active material is preferably in the formof a powder having a particle diameter of 1 to 100 μm and an averageparticle diameter of about 10 μm, in order that it can be uniformlydispersed in a coating layer. One or more of these negative activematerials may be used alone or in combination.

In particular, a lithium secondary battery having a high dischargevoltage of about 4 V can be obtained using LiCoO₂ and the carbonaceousmaterial as the positive and negative active materials, respectively.

Based on the amount of the components other than the solvent (based onthe amount of the solid components), the content of the positive ornegative active material in the coating composition is generally from 90to 98.5% by weight, preferably from 93 to 98.5% by weight, morepreferably from 96 to 98.5% by weight, in terms of achieving highcapacity.

The binder may be any conventional binder, for example, includingthermoplastic resins. Specific examples of the applicable binder includepolyester resins, polyamide resins, polyacrylic ester resins,polycarbonate resins, polyurethane resins, cellulose resins, polyolefinresins, polyvinyl resins, fluorocarbon resins, and polyimide resins. Inthis case, an acrylate monomer or oligomer having an introduced reactivefunctional group can be blended into the binder. Other examples of theapplicable binder include rubber-based resins, thermosetting resins suchas acrylic resins and urethane resins, ionizing radiation-curable resinscomprising of an acrylate monomer, an acrylate oligomer or a mixturethereof, and mixtures of the above described various resins.

Based on the amount of the solid components, the content of the binderin the coating composition is generally from 0.5 to 10% by weight,preferably from 1 to 5% by weight or preferably from 1.5 to 3% by weightin terms of achieving high capacity.

The positive or negative active material layer coating composition mayalso contain an electrically conductive agent. For example, acarbonaceous material such as graphite, carbon black or acetylene blackis optionally used as the electrically conductive agent. Based on theamount of the solid components, the content of the electricallyconductive agent in the coating composition is generally from 1 to 3% byweight.

The solvent for use in preparation of the positive or negative activematerial layer coating composition may be an organic solvent such astoluene, methyl ethyl ketone, N-methyl-2-pyrrolidone, or any mixturethereof; or water. The content of the solvent in the coating compositionis generally from 10 to 60% by weight, so that the coating liquid can beprepared in the form of a slurry.

The positive or negative active material layer coating composition maybe prepared in the form of a slurry by adding an appropriately selectedpositive or negative active material, a binder and any other componentto an appropriate solvent, and mixing and dispersing them in adispersing machine such as a homogenizer, a ball mill, a sand mill, aroll mill, and a planetary mixer.

The positive or negative active material layer coating compositionprepared as described above is applied to one side or both sides of acollector, which is a base material, and dried to form a positive ornegative active material layer. In general, an aluminum foil ispreferably used as a collector for the positive electrode plate. Acopper foil such as an electrolytic copper foil and a rolled copper foilis preferably used as a collector for the negative electrode plate. Thecollector generally has a thickness of about 5 to about 50 μm.

Any coating method may be used to apply the positive or negative activematerial layer coating composition. A coating method capable of forminga thick coating layer is suitable, such as slide die coating, slit diecoating, comma direct coating, and comma reverse coating. When arelatively thin active material layer is required, gravure coating,gravure reverse coating or the like may be used in the applicationprocess. The active material layer may be formed by repeatingapplication and drying more than once.

In the drying process, the heat source may be hot air, infraredradiation, microwave, high-frequency wave, or any combination thereof.In the drying process, heat maybe released from a heated metal roller orsheet for supporting or pressing the collector and used for drying. Byradiating electron beams or radioactive rays after the drying, thebinders are caused to crosslink-react so that the active material layercan be obtained. Application and drying may be repeated more than once.

In addition, the resulting positive or negative active material layermay be pressed so that the active material layer can have a higherdensity or improved homogeneity or exhibit increased adhesion to thecollector.

For example, the press working is performed using a metal roll, anelastic roll, a heating roll, a sheet pressing machine, or the like. Inthe present invention, the press-working may be performed at roomtemperature or raised temperature as far as the press temperature islower than the temperature for drying the coating layer of the activematerial layer. The press-working is usually performed at roomtemperature (typically ranging from 15 to 35° C.)

Roll press is preferred, because it allows continuous press working of along sheet-shaped negative electrode plate. The roll press may be staticpress or constant pressure press. The line speed of the press isgenerally from 5 to 50 m/min. When the pressure of the roll-press iscontrolled by line pressure, the line pressure, which is adjusteddependently on the diameter of the pressing roll, is usually set to 0.5kgf/cm to 2 tf/cm.

When sheet pressing is performed, the pressure is generally controlledin the range from 4903 to 73550 N/cm² (500 to 7500 kgf/cm²), preferablyin the range from 29420 to 49033 N/cm² (3000 to 5000 kgf/cm²). If thepressing pressure is too low, the active material layer can be lesshomogeneous. If the pressing pressure is too high, the electrode plateitself including the collector can be broken. The active material layermay be pressed once so as to have the desired thickness or may bepressed several times for the purpose of improving the homogeneity.

The coating amount of the positive or negative active material layer isgenerally from 100 to 400 g/m². The thickness of the coating isgenerally set in the range from 50 to 200 μm after the drying andpressing processes. The density of the negative active material layermay be about 1.0 g/cc after the coating process but can be increased toat least 1.5 g/cc (generally about 1.5 to 1.75 g/cc) after the pressingprocess. When the press working is performed without any trouble so asto improve the volume energy density, a high capacity battery can beproduced.

The resulting active material layer of the electrode plate contains atleast the positive or negative active material and the binder andoptionally the electrically conductive agent and/or any other component.After the drying process, the content of each component in the activematerial layer may be the same as the above content based on the amountof the solid components of the active material layer coatingcomposition.

According to the present invention, one or more slits are formed in theresulting active material layer. Thus, even when the electrode platesare wound at high density, there is no projection portion so that alocally applied load can be avoided, and the electrolyte can easilyinfiltrate into the active material layer.

The slit or slits of the positive or negative active material layer maybe formed in any pattern. For example, as shown in the FIG. 1, the slits3 maybe formed in the form of lines inclined against the windingdirection 2 of the electrode plate in the active material layer 1. Forother examples, as shown in the FIG. 2, the slits may be formedperpendicular (FIG. 2(a)) or parallel (FIG. 2(b)) to the windingdirection 2 of the electrode plate or formed by the intersection oflines (FIG. 2(c)) inclined against the winding direction 2 of theelectrode plate in the active material layer 1. The slit or slits mayalso be formed in a curved pattern. For example, the slit or slits maybe formed using a rotary die unit as shown in FIG. 3 or the like. Itshould be noted that the collector serving as a substrate for the activematerial layer should not be damaged when the slit or slits are formedin the active material layer.

In terms of infiltration, the depth of the slit is preferably about 5 μmor more, more preferably about 8 μm or more, particularly preferablyabout 10 μm or more. In terms of infiltration, the width of the slit ispreferably about 10 μm or more, more preferably from about 10 to about50 μm, particularly preferably from about 15 to about 40 μm.

A too wide spacing between the slits cannot improve the infiltration ofthe electrolyte, while a too narrow spacing between the slits can makethe active material layer brittle. Thus, the distance 4 between theadjacent slits is preferably from about 0.1 to about 10 mm, morepreferably from about 1 to about 10 mm, particularly preferably fromabout 2 to about 5 mm.

According to the above description, the inventive electrode plate fornonaqueous electrolyte secondary batteries can be obtained, andnonaqueous electrolyte secondary batteries are produced using thepresent electrode plate.

The nonaqueous electrolyte secondary battery of the present inventioncomprises a positive electrode plate and a negative electrode plate, inwhich at least one of the positive and negative plates comprises theelectrode plate for a nonaqueous electrolyte secondary battery of thepresent invention; preferably, both positive and negative platescomprise the electrode plate for a nonaqueous electrolyte secondarybattery of the present invention.

The electrode plate for a nonaqueous electrolyte secondary batteryaccording to the present invention is used as at least one of thepositive and negative electrode plates, which are wound into a swirlform with a separator such as a porous polyethylene film interposedtherebetween and inserted into a packing container. After the insertion,a lead is connected between a terminal connection part of the positiveelectrode plate (an exposed surface of the collector) and a positiveterminal provided on the upper surface of the packing container, whileanother lead is connected between a terminal connection part of thenegative electrode plate (another exposed surface of the collector) anda negative terminal provided on the bottom surface of the packingcontainer. The packing container is then filled with a liquid nonaqueouselectrolyte and sealed so that a nonaqueous electrolyte secondarybattery comprising the electrode plate according to the presentinvention is completed.

In this secondary battery, the winding density of the electrode platecan be increased for the purpose of increasing the capacity, because theelectrode plates packed inside can facilitate infiltration of a liquidelectrolyte even when wound at high density and can have high stabilityof quality. Therefore, in this secondary battery a larger amount of theactive material can be stored in the limited volume, so that the batterycan stably offer high capacity and high quality performance for a longtime.

When a lithium secondary battery is produced, a solution of a lithiumsalt (which is a solute) in an organic solvent is used as the liquidnonaqueous electrolyte. The lithium salt may be an inorganic lithiumsalt such as LiClO₄, LiBF₄, LiPF₆, LiAsF₆, LiCl, and LiBr; or an organiclithium salt such as LiB(C₆H₅)₄, LiN(SO₂CF₃)₂, LiC(SO₂CF₃)₃, LiOSO₂CF₃,LiOSO₂C₂F₅, LiOSO₂C₃F₇, LiOSO₂C₄F₉, LiOSO₂C₅F₁₁, LiOSO₂C₆F₁₃, andLiOSO₂C₇F₁₅.

Examples of the organic solvent for use in dissolving the lithium saltinclude cyclic esters, chain esters, cyclic ethers, and chain ethers.Specific examples of the cyclic esters include ethylene carbonate,propylene carbonate, butylene carbonate, γ-butyrolactone, vinylenecarbonate, 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, andγ-valerolactone.

Examples of the chain esters include dimethyl carbonate, diethylcarbonate, dibutyl carbonate, dipropyl carbonate, methyl ethylcarbonate, methyl butyl carbonate, methyl propyl carbonate, ethyl butylcarbonate, ethyl propyl carbonate, butyl propyl carbonate, alkylpropionate, dialkyl malonate, and alkyl acetate.

Examples of the cyclic ethers include tetrahydrofuran,alkyltetrahydrofuran, dialkyltetrahydrofuran, alkoxytetrahydrofuran,dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, and1,4-dioxolane.

Examples of the chain ethers include 1,2-dimethoxyethane,1,2-diethoxyethane, diethyl ether, ethylene glycol dialkyl ether,diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, andtetraethylene glycol dialkyl ether.

As described above, in the electrode plate for a nonaqueous electrolytesecondary battery according to the present invention, the slit or slitsof the active material layer ensure a path or paths for a liquidelectrolyte even at high winding density and can increase the surfacearea of the active material layer. Even when electrode plates wound athigh density are placed in a battery case, the liquid electrolyte caneasily infiltrate into the active material layer so that charges canrapidly move between the electrodes and that a high voltage or a highcurrent can be produced. In addition, the active material layer has noprojection portion and thus can be free from a locally applied load.Therefore, the electrode can be prevented from being ruptured byexpansion and contraction of the volume during charge and dischargecycles and can exhibit high stability of quality. Thus, the electrodeplate for a nonaqueous electrolyte secondary battery of the inventioncan suppress the production of defectives and can achieve high capacityand high quality.

In addition, in the nonaqueous electrolyte secondary battery accordingto the present invention, the winding density of the electrode plate canbe increased for the purpose of increasing the capacity, because theelectrode plates packed inside can facilitate infiltration of a liquidelectrolyte even when wound at high density and can have high stabilityof quality. Therefore, in this secondary battery a larger amount of theactive material can be stored in the limited volume, so that the batterycan stably offer high capacity and high quality performance for a longtime.

EXAMPLES Example 1

A positive active material layer coating composition was prepared bydispersing and mixing 100 parts by weight of LiCoO₂ (positive activematerial), 2.5 parts by weight of acetylene black (electricallyconductive agent for positive electrode), 2 parts by weight ofpolyvinylidene fluoride (binder for positive electrode), and 45 parts byweight of N-methyl pyrrolidone (solvent) in a planetary disperser. Thepositive active material layer coating composition was applied to bothsides of a 15 μm thick aluminum foil so as to have a dry coating amountof about 250 g/m² per one side. Thereafter, the coating was dried andpressed so that a positive electrode plate with a coating film densityof 3.7 g/cc was obtained. Slits were then formed in the positiveelectrode plate through a rotary die unit. The slits were formed with adepth of 10 μm, a width of 10 μm. And a distance between the adjacentslits was 5 mm. The positive electrode plate was cut so as to have awidth of 56 mm.

On the other hand, a negative active material layer coating compositionwas prepared by dispersing and mixing 100 parts by weight of graphite(negative active material), 5 parts by weight of polyvinylidene fluoride(binder for negative electrode), and 70 parts by weight ofN-methylpyrrolidone (solvent) in a planetary disperser. The negativeactive material layer coating composition was applied to both sides of a10 μm thick copper foil so as to have a dry coating amount of about 100g/m² per one side. Thereafter, the coating was dried and pressed so thata negative electrode plate was obtained. The resulting positive andnegative electrode plates were tightly wound with a separator interposedtherebetween to be inserted into a packing container. And, aselectrolyte, a solution of 1 M LiPF₆ in ethylene carbonate/methyl ethylcarbonate (1/1) was injected thereto.

Example 2

The process of Example 1 was performed except that through the rotarydie unit, the slits was formed with a depth of 20 μm, a width of 20 μmand a distance between the adjacent slits of 5 mm in the positiveelectrode for use, after the press.

Example 3

The process of Example 1 was performed except that through the rotarydie unit, the slits was formed with a depth of 3 μm, a width of 5 μm anda distance between the adjacent slits of 5 mm in the positive electrodefor use, after the press.

Comparative Example 1

The process of Example 1 was performed except that no slit was formed inthe positive electrode plate for use, after the press.

(Results of Evaluation)

The electrode plate obtained in each of Examples and Comparative Examplewas evaluated in terms of infiltration of the liquid electrolyte asshown below. In each of Examples 1 to 3 with theelectrode plate of thepresent invention, the active material layer of the electrode plate hadslits according to the present invention, and thus the electrode platewas able to be wound without any locally applied force. In addition, theliquid electrolyte easily infiltrated, even when the electrodes werewound at high density. In Examples 1 and 2 with a slit depth of at least5 μm, infiltration characteristic of the electrolyte was particularlygood. In Comparative Example 1 with no the electrode plate of theinvention, the active material layer of the electrode plate had no slit,and thus infiltration characteristic of the electrolyte was poor, whenthe electrode was wound at the same density as in each of Examples.

1. An electrode plate for a nonaqueous electrolyte secondary battery, comprising a collector and an active material layer formed on at least one side of the collector, wherein the active material layer has one or more slits.
 2. The electrode plate according to claim 1, wherein the slit has a depth of about 5 μm or more.
 3. The electrode plate according to claim 1, wherein a distance between the adjacent slits is from about 0.1 mm to about 10 mm.
 4. A nonaqueous electrolyte secondary battery, comprising the electrode plate according to claim
 1. 